CN107640775B - Method for preparing ZSM-5 molecular sieve by using solid waste - Google Patents

Method for preparing ZSM-5 molecular sieve by using solid waste Download PDF

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CN107640775B
CN107640775B CN201710967267.1A CN201710967267A CN107640775B CN 107640775 B CN107640775 B CN 107640775B CN 201710967267 A CN201710967267 A CN 201710967267A CN 107640775 B CN107640775 B CN 107640775B
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李素芹
张昌泉
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University of Science and Technology Beijing USTB
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Abstract

本发明涉及一种利用固体废弃物制备ZSM‑5分子筛的方法,具体是涉及以稻壳灰、铁尾矿以及金尾矿等固体废弃物为原料提供合成ZSM‑5分子筛所需要的全部或部分硅源和铝源,同时在无溶剂和NaOH的参与下合成ZSM‑5分子筛制备工艺。将硅源、铝源、Na2CO3∙10H2O、模板剂或晶种混合后直接置入反应釜恒温晶化得到ZSM‑5分子筛,该方法将Na2CO3∙10H2O应用在以固体废弃物为原料合成ZSM‑5分子筛的工艺中,合成过程中无二次污染。该发明以稻壳灰、铁尾矿、金尾矿等固体废弃物为原料利用无溶剂法合成ZSM‑5分子筛,工艺简单、适用范围广,不仅可以缓解固体废弃物带来的环境问题,而且可实现固体废弃物的高附加值利用。

Figure 201710967267

The present invention relates to a method for preparing ZSM-5 molecular sieve by utilizing solid waste, in particular to providing all or part of all or part of the synthesis of ZSM-5 molecular sieve by using solid wastes such as rice husk ash, iron tailings and gold tailings as raw materials Silicon source and aluminum source, and the preparation process for synthesizing ZSM-5 molecular sieve without the participation of solvent and NaOH at the same time. The silicon source, aluminum source, Na 2 CO 3 ∙10H 2 O, template agent or crystal seed are mixed and directly placed in a reactor for constant temperature crystallization to obtain ZSM-5 molecular sieve. This method applies Na 2 CO 3 ∙ 10H 2 O to the In the process of synthesizing ZSM-5 molecular sieve from solid waste as raw material, there is no secondary pollution during the synthesis process. The invention uses solid wastes such as rice husk ash, iron tailings, gold tailings and other solid wastes as raw materials to synthesize ZSM-5 molecular sieves by a solvent-free method. The process is simple and the scope of application is wide, which can not only alleviate the environmental problems caused by solid wastes, but also High value-added utilization of solid waste can be achieved.

Figure 201710967267

Description

一种利用固体废弃物制备ZSM-5分子筛的方法A method for preparing ZSM-5 molecular sieve by using solid waste

技术领域technical field

本发明属于分子筛制备以及环境保护领域。具体是涉及以稻壳灰、铁尾矿以及金尾矿提供合成ZSM-5分子筛所需要的全部或部分硅源和铝源,同时在无溶剂和NaOH的参与下合成含有多级孔ZSM-5分子筛的利用固体废弃物制备ZSM-5分子筛的方法。The invention belongs to the field of molecular sieve preparation and environmental protection. Specifically, rice husk ash, iron tailings and gold tailings are used to provide all or part of the silicon and aluminum sources required for the synthesis of ZSM-5 molecular sieves, and at the same time, without the participation of solvents and NaOH, the synthesis of ZSM-5 containing hierarchical pores A method for preparing ZSM-5 molecular sieve by using solid waste of molecular sieve.

背景技术Background technique

ZSM-5分子筛自1972年由美国Mobil公司首次报道(USP3702886)以来,由于其独特的孔道结构和择形催化作用,已经在许多炼油和化工过程中得到了应用,其制备方法也在不断改进,由最初的采用有机胺模板剂合成,到后来的无胺法合成,使ZSM-5的制造成本明显降低,再通过对合成后ZSM-5分子筛产物的后改性处理等技术的进步,使ZSM-5分子筛的应用领域不断扩大。例如,早期应用于炼油工业的流化催化裂化(FCC)催化剂均不采用ZSM-5分子筛,而当今的FCC催化剂多数添加有ZSM-5分子筛,用以提高催化剂性能,进而改善产品分布。由于FCC催化剂是一类需要量很大的催化剂,仅在中国市场上年消耗量就达到数万吨,这导致了对ZSM-5分子筛需求量的增加,同时也要求进一步降低ZSM-5分子筛的生产成本。Since ZSM-5 molecular sieve was first reported by American Mobil Corporation in 1972 (USP3702886), due to its unique pore structure and shape-selective catalysis, it has been applied in many oil refining and chemical processes, and its preparation method has been continuously improved. From the initial synthesis using organic amine template agent to the subsequent synthesis without amine, the manufacturing cost of ZSM-5 is significantly reduced. The application field of -5 molecular sieve is expanding continuously. For example, none of the early fluid catalytic cracking (FCC) catalysts used in the refining industry used ZSM-5 molecular sieves, while most of today's FCC catalysts have ZSM-5 molecular sieves added to improve catalyst performance and thus product distribution. Since FCC catalyst is a kind of catalyst with great demand, the annual consumption in the Chinese market alone reaches tens of thousands of tons, which leads to an increase in the demand for ZSM-5 molecular sieve, and also requires further reduction of ZSM-5 molecular sieve. Cost of production.

从另一方面讲,包括ZSM-5分子筛在内的沸石分子筛在FCC催化剂等催化剂中的作用是作为活性组分,活性组分的良好分散对催化剂来说是很重要的,这样可以提高活性组分的利用效率。提高分子筛活性组分在催化剂中的分散度的一个重要措施,就是使用晶体尺寸尽量小的分子筛产品。众所周知,纳米晶体或引入介孔的分子筛,由于表面面积、反应的活性位点和分子扩散的增加,可以优化分子筛在催化和吸附应用等领域提供额外潜力,所以纳米晶体的分子筛对于制造高性能催化剂是必要的。然而,现有的无溶剂法合成分子筛晶体的大小通常在几微米的范围,所以利用无溶剂法合成纳米晶体分子筛是一个巨大的挑战。On the other hand, the role of zeolite molecular sieves, including ZSM-5 molecular sieves, in catalysts such as FCC catalysts is as active components, and good dispersion of active components is very important for catalysts, which can improve the active components. the utilization efficiency of points. An important measure to improve the dispersion of active molecular sieve components in the catalyst is to use molecular sieve products with as small a crystal size as possible. It is well known that nanocrystals or molecular sieves incorporating mesopores can optimize molecular sieves due to the increase in surface area, reactive sites for reactions, and molecular diffusion, providing additional potential in fields such as catalysis and adsorption applications, so nanocrystalline molecular sieves are useful for the fabrication of high-performance catalysts. necessary. However, the size of the existing solvent-free synthesis of molecular sieve crystals is usually in the range of several microns, so it is a huge challenge to use the solvent-free method to synthesize nanocrystalline molecular sieves.

通常制备ZSM-5分子筛的方法是采用碱性的硅铝凝胶体系合成。体系由氧化钠、氧化铝、氧化硅和水组成。用于合成原料的硅源一般为水玻璃、硅胶等,铝源一般为硫酸铝、铝酸钠等。20世纪80年代以前一般使用季铵盐或其他有机胺作为模板剂来合成ZSM-5分子筛(简称“有胺法”),由于季铵盐等有机模板剂价格较高,20世纪80年代以后出现了利用ZSM-5分子筛晶种合成ZSM-5分子筛的技术(即“晶种法”或“无胺法”),使得ZSM-5分子筛的制备成本明显降低。The usual method for preparing ZSM-5 molecular sieve is to use an alkaline silica-alumina gel system to synthesize it. The system consists of sodium oxide, aluminum oxide, silicon oxide and water. The silicon source used for synthesizing raw materials is generally water glass, silica gel, etc., and the aluminum source is generally aluminum sulfate, sodium aluminate, etc. Before the 1980s, quaternary ammonium salts or other organic amines were generally used as templates to synthesize ZSM-5 molecular sieves (referred to as "amine method"). The technology of synthesizing ZSM-5 molecular sieve by using ZSM-5 molecular sieve seed crystal (ie "seed crystal method" or "amine-free method") makes the preparation cost of ZSM-5 molecular sieve significantly reduced.

ZSM-5分子筛合成工艺基本上采用水热法、干胶转化法、无溶剂法等。水热法合成体系需要含有大量的碱性溶液,在用反应釜合成过程之前需要将原料进行搅拌、陈化等过程,降低分子筛的合成效率。干胶转化法是一种固相合成分子筛的方法,包含气相转化法和蒸汽辅助法,需要将硅源、铝源与水混合制备凝胶,去除水后的干凝胶用于制备分子筛。以上这些方法在制备ZSM-5分子筛过程中不能完全避免溶剂的使用,产生大量的含碱废水并且降低分子筛合成设备的空间利用率。无溶剂法是指在分子筛制备工艺过程中不使用任何溶剂,目前无溶剂法主要利用纯化学试剂为原料,经过简单混合研磨后直接置入反应釜在一定温度下密封静置合成,此工艺简单、设备利用率高,但是合成原料中含有NH4F、NH4Cl等对环境有害的物质,不适用于工业大规模应用,并且目前尚无以固体废弃物为原料利用无溶剂法合成分子筛的报道。The synthesis process of ZSM-5 molecular sieve basically adopts hydrothermal method, dry glue conversion method, solvent-free method and so on. The hydrothermal synthesis system needs to contain a large amount of alkaline solution, and the raw materials need to be stirred and aged before the synthesis process in the reactor, which reduces the synthesis efficiency of molecular sieves. The dry gel conversion method is a method of solid-phase synthesis of molecular sieves, including gas-phase conversion method and steam-assisted method. It is necessary to mix silicon source, aluminum source and water to prepare gel, and the dry gel after water removal is used to prepare molecular sieve. The above methods cannot completely avoid the use of solvents in the process of preparing ZSM-5 molecular sieves, generate a large amount of alkali-containing wastewater and reduce the space utilization rate of molecular sieve synthesis equipment. Solvent-free method means that no solvent is used in the preparation process of molecular sieve. At present, the solvent-free method mainly uses pure chemical reagents as raw materials. , The utilization rate of equipment is high, but the synthetic raw materials contain NH 4 F, NH 4 Cl and other substances that are harmful to the environment, which are not suitable for large-scale industrial applications, and there is no solvent-free synthesis of molecular sieves using solid waste as raw materials. report.

发明内容SUMMARY OF THE INVENTION

为了解决上述问题,本发明的主要目的在于提供一种利用更廉价、原料来源更广泛的固体废弃物作为合成原料,利用无溶剂法将原料混合后直接置入反应釜在一定温度下密封静置合成,原料中无NH4F、NH4Cl等对环境有害的物质,实现绿色、低成本合成具有纳米晶体多级孔ZSM-5分子筛的方法。In order to solve the above-mentioned problems, the main purpose of the present invention is to provide a kind of solid waste that utilizes cheaper and more extensive sources of raw materials as synthetic raw materials, and uses a solvent-free method to mix the raw materials and directly put them into a reaction kettle and seal them at a certain temperature. Synthesis, there is no NH 4 F, NH 4 Cl and other substances harmful to the environment in the raw materials, and a green and low-cost method for synthesizing the ZSM-5 molecular sieve with nanocrystalline hierarchical pores is realized.

原料中包含稻壳灰、金尾矿和铁尾矿等固体废弃物,稻壳灰中SiO2含量达到90%左右,且为非晶体,可直接作为硅源制备ZSM-5分子筛;原料中铁尾矿和金尾矿的成分主要含有石英、钠长石、钾长石、钙长石、磁铁矿、黄铁矿、堇青石、滑石以及伊利石,金尾矿和铁尾矿成分复杂,含有多种硅酸盐矿物以及磁铁矿和黄铁矿杂质,SiO2含量占60%以上,需要将金尾矿和铁尾矿中硅酸盐矿物活化。The raw materials include solid wastes such as rice husk ash, gold tailings and iron tailings. The content of SiO2 in rice husk ash reaches about 90%, and it is amorphous, which can be directly used as a silicon source to prepare ZSM-5 molecular sieve; iron tailings in the raw material The composition of and gold tailings mainly contains quartz, albite, potassium feldspar, anorthite, magnetite, pyrite, cordierite, talc and illite. The composition of gold tailings and iron tailings is complex and contains many silicate minerals and impurities of magnetite and pyrite, the content of SiO2 accounts for more than 60%, and the silicate minerals in gold tailings and iron tailings need to be activated.

本发明的技术方案是:一种利用固体废弃物制备ZSM-5分子筛的方法,该方法具体包括以下步骤:The technical scheme of the present invention is: a method for preparing ZSM-5 molecular sieve by utilizing solid waste, the method specifically comprises the following steps:

步骤1:以固体废弃物为硅源,将硅源、十水碳酸钠、铝源物质和模板剂按照一定的比例混合,混合研磨1~10分钟;Step 1: take the solid waste as the silicon source, mix the silicon source, sodium carbonate decahydrate, aluminum source material and template agent according to a certain ratio, and mix and grind for 1-10 minutes;

步骤2:将步骤1得到的混合物置入不锈钢反应釜,升温至100~200℃,晶化3~96小时,晶化结束后,急速冷却、洗涤、干燥滤饼,得到含有多级孔结构的ZSM-5分子筛。Step 2: Put the mixture obtained in Step 1 into a stainless steel reactor, heat up to 100-200°C, and crystallize for 3-96 hours. After the crystallization is completed, rapidly cool, wash, and dry the filter cake to obtain a filter cake containing a hierarchical pore structure. ZSM-5 molecular sieve.

进一步,所述硅源、十水碳酸钠、铝源物质和模板剂的比例为:n(TPABr)/n(SiO2)=0.1~2.0;n(Na2CO3·10H2O)/n(SiO2)=0.1~10;n(SiO2)/n(Al2O3)=20~+∞。Further, the ratio of the silicon source, sodium carbonate decahydrate, aluminum source material and template agent is: n(TPABr)/n(SiO 2 )=0.1-2.0; n(Na 2 CO 3 ·10H 2 O)/n (SiO 2 )=0.1 to 10; n(SiO 2 )/n(Al 2 O 3 )=20 to +∞.

进一步,所述固体废弃物为稻壳灰、铁尾矿或金尾矿,当采用铁尾矿和金尾矿时,需现将所述铁尾矿和金尾矿进行活化处理。Further, the solid waste is rice husk ash, iron tailings or gold tailings. When iron tailings and gold tailings are used, the iron tailings and gold tailings need to be activated now.

进一步,所述活化处理工艺为:采用碱烧结方式对金尾矿和铁尾矿进行活化处理,n(NaOH)/n(SiO2)=1~4,活化处理温度为200~1000℃,活化处理时间为1~10小时。将活化后的碱烧结产物与水混合搅拌50-70分钟,产物分为可溶于水物质与不溶于水固体,固液不分离直接调节溶液pH=9,静置6~24小时,80℃恒温干燥得到固体粉末。Further, the activation treatment process is as follows: the gold tailings and the iron tailings are activated by means of alkali sintering, n(NaOH)/n(SiO 2 )=1~4, the activation treatment temperature is 200~1000°C, and the activation The treatment time is 1 to 10 hours. The activated alkali sintered product is mixed with water and stirred for 50-70 minutes, the product is divided into water-soluble substances and water-insoluble solids, the solution pH is directly adjusted without separation of solid and liquid, and the solution is left standing for 6 to 24 hours at 80°C Dry at constant temperature to obtain solid powder.

进一步,所述铁尾矿或金尾矿的成分:所述铁尾矿或金尾矿的成分主要含有石英、钠长石、钾长石、钙长石、磁铁矿、黄铁矿、堇青石、滑石以及伊利石。Further, the composition of the iron tailings or gold tailings: the composition of the iron tailings or gold tailings mainly contains quartz, albite, potassium feldspar, anorthite, magnetite, pyrite, and cordier. Bluestone, talc and illite.

进一步,所述铁尾矿和金尾矿活化前不经过酸浸提纯处理,避免含酸废液的产生。Further, the iron tailings and gold tailings are not subjected to acid leaching and purification treatment before activation, so as to avoid the generation of acid-containing waste liquid.

本发明提供的合成ZSM-5分子筛及制备方法具有如下特点:The synthetic ZSM-5 molecular sieve and preparation method provided by the invention have the following characteristics:

(1)扩展了利用无溶剂法合成ZSM-5分子筛的原料范围,为稻壳灰、铁尾矿和金尾矿等固体废弃物找到了新用途,降低了制备ZSM-5分子筛的原料成本。(1) The range of raw materials for synthesizing ZSM-5 molecular sieve by solvent-free method was expanded, new uses were found for solid wastes such as rice husk ash, iron tailings and gold tailings, and the cost of raw materials for preparing ZSM-5 molecular sieve was reduced.

(2)按照本发明的方法制备ZSM-5分子筛,反应混合物的原料物质中不含溶剂和氢氧化钠。此方法可以提高分子筛合成设备的利用率,降低分子筛生产成本,减少分子筛生产过程中的污染。(2) ZSM-5 molecular sieve is prepared according to the method of the present invention, and the raw material of the reaction mixture does not contain solvent and sodium hydroxide. The method can improve the utilization rate of the molecular sieve synthesis equipment, reduce the production cost of the molecular sieve, and reduce the pollution in the production process of the molecular sieve.

(3)本发明所提供的ZSM-5分子筛结晶度高,具有纳米晶体,可以缩短反应物和产物分子在分子筛晶内扩散的路径,提高催化生产效率。(3) The ZSM-5 molecular sieve provided by the present invention has high crystallinity and nanocrystals, which can shorten the diffusion path of reactant and product molecules in the molecular sieve crystal and improve the catalytic production efficiency.

(4)相比用传统方法合成的ZSM-5分子筛,使用本发明制备的ZSM-5分子筛产品含有多级孔结构。(4) Compared with the ZSM-5 molecular sieve synthesized by the traditional method, the ZSM-5 molecular sieve product prepared by the present invention contains a hierarchical pore structure.

附图说明Description of drawings

图1为本发明实施例1以稻壳灰为原料合成的ZSM-5分子筛的X射线衍射(XRD)谱图。Fig. 1 is the X-ray diffraction (XRD) spectrum of ZSM-5 molecular sieve synthesized with rice husk ash as raw material in Example 1 of the present invention.

图2为本发明一种利用固体废弃物制备ZSM-5分子筛的方法的流程框图。Fig. 2 is a flow chart of a method for preparing ZSM-5 molecular sieve from solid waste according to the present invention.

具体实施方式Detailed ways

下面结合具体实施例对本发明的技术方案做进一步说明。The technical solutions of the present invention will be further described below with reference to specific embodiments.

本发明一种利用固体废弃物制备ZSM-5分子筛的方法,该方法具体包括以下步骤:A method of utilizing solid waste to prepare ZSM-5 molecular sieve of the present invention specifically comprises the following steps:

步骤1:以固体废弃物为硅源,将硅源、十水碳酸钠、铝源物质和模板剂按照一定的比例混合,混合研磨1~10分钟;Step 1: take the solid waste as the silicon source, mix the silicon source, sodium carbonate decahydrate, aluminum source material and template agent according to a certain ratio, and mix and grind for 1-10 minutes;

步骤2:将步骤1得到的混合物置入不锈钢反应釜,升温至100~200℃,晶化3~96小时,晶化结束后,急速冷却、洗涤、干燥滤饼,得到含有多级孔结构的ZSM-5分子筛。Step 2: Put the mixture obtained in Step 1 into a stainless steel reactor, heat up to 100-200°C, and crystallize for 3-96 hours. After the crystallization is completed, rapidly cool, wash, and dry the filter cake to obtain a filter cake containing a hierarchical pore structure. ZSM-5 molecular sieve.

进一步,所述硅源、十水碳酸钠、铝源物质和模板剂的比例为:n(TPABr)/n(SiO2)=0.1~2.0;n(Na2CO3·10H2O)/n(SiO2)=0.1~10;n(SiO2)/n(Al2O3)=20~+∞。Further, the ratio of the silicon source, sodium carbonate decahydrate, aluminum source material and template agent is: n(TPABr)/n(SiO 2 )=0.1-2.0; n(Na 2 CO 3 ·10H 2 O)/n (SiO 2 )=0.1 to 10; n(SiO 2 )/n(Al 2 O 3 )=20 to +∞.

进一步,所述固体废弃物为稻壳灰、铁尾矿或金尾矿,当采用铁尾矿和金尾矿时,需现将所述铁尾矿和金尾矿进行活化处理。Further, the solid waste is rice husk ash, iron tailings or gold tailings. When iron tailings and gold tailings are used, the iron tailings and gold tailings need to be activated now.

进一步,所述活化处理工艺为:采用碱烧结方式对金尾矿和铁尾矿进行活化处理,n(NaOH)/n(SiO2)=1~4,活化处理温度为200~1000℃,活化处理时间为1~10小时。将活化后的碱烧结产物与水混合搅拌50-70分钟,产物分为可溶于水物质与不溶于水固体,固液不分离直接调节溶液pH=9,静置6~24小时,80℃恒温干燥得到固体粉末。Further, the activation treatment process is as follows: the gold tailings and the iron tailings are activated by means of alkali sintering, n(NaOH)/n(SiO 2 )=1~4, the activation treatment temperature is 200~1000°C, and the activation The treatment time is 1 to 10 hours. The activated alkali sintered product is mixed with water and stirred for 50-70 minutes, the product is divided into water-soluble substances and water-insoluble solids, the solution pH is directly adjusted without separation of solid and liquid, and the solution is left standing for 6 to 24 hours at 80°C Dry at constant temperature to obtain solid powder.

进一步,所述铁尾矿或金尾矿的成分:所述铁尾矿或金尾矿的成分主要含有石英、钠长石、钾长石、钙长石、磁铁矿、黄铁矿、堇青石、滑石以及伊利石,所述铁尾矿或金尾矿中硅酸盐的含量不低于50%。Further, the composition of the iron tailings or gold tailings: the composition of the iron tailings or gold tailings mainly contains quartz, albite, potassium feldspar, anorthite, magnetite, pyrite, and cordier. Bluestone, talc and illite, the content of silicate in the iron tailings or gold tailings is not less than 50%.

进一步,所述铁尾矿和金尾矿活化前不经过酸浸提纯处理,避免含酸废液的产生。Further, the iron tailings and gold tailings are not subjected to acid leaching and purification treatment before activation, so as to avoid the generation of acid-containing waste liquid.

进一步,所述多级孔结构的ZSM-5分子筛还可以作为ZSM-5分子筛的晶种使用。Further, the ZSM-5 molecular sieve with the hierarchical pore structure can also be used as a seed crystal of the ZSM-5 molecular sieve.

实施例1:Example 1:

以200目稻壳灰为原料,取2g稻壳灰,依次加入0.2g铝酸钠,2.5g Na2CO3·10H2O以及0.2g TPABr,放置在研钵中研磨混合5分钟,将混合物置入密封的不锈钢反应釜中升温到100℃恒温静置晶化72小时。晶化结束后,急速冷却、洗涤、干燥滤饼,得到晶化产物。经X射线衍射(XRD)测试,其产物属于ZSM-5分子筛,ZSM-5分子筛晶体尺寸为40~200nm,原料中Fe、Mn杂质进入分子筛骨架,得到的ZSM-5分子筛产品同时含有微孔和介孔。其XRD物相图见图1。Take 200 mesh rice husk ash as raw material, take 2 g of rice husk ash, add 0.2 g of sodium aluminate, 2.5 g of Na 2 CO 3 ·10H 2 O and 0.2 g of TPABr in turn, place it in a mortar and grind and mix for 5 minutes, and the mixture is mixed. It was placed in a sealed stainless steel reaction kettle and heated to 100°C for 72 hours at a constant temperature for crystallization. After the crystallization, the filter cake was rapidly cooled, washed and dried to obtain a crystallized product. The X-ray diffraction (XRD) test shows that the product belongs to ZSM-5 molecular sieve. The crystal size of ZSM-5 molecular sieve is 40-200 nm. The Fe and Mn impurities in the raw material enter the molecular sieve framework. The obtained ZSM-5 molecular sieve product contains both micropores and mesoporous. Its XRD phase diagram is shown in Figure 1.

实施例2:Example 2:

以铁尾矿为原料,SiO2含量为67%,取10g铁尾矿在马弗炉中500℃活化3小时,活化产物水浸1小时,调节滤液pH为9,静置12小时,烘干得到粉末作为ZSM-5分子筛合成原料。将2g滤渣、0.2g铝酸钠、2.5g Na2CO3·10H2O以及0.2g TPABr放置在研钵中研磨混合5分钟,将混合物置入密封的不锈钢反应釜中升温到100℃恒温静置晶化72小时。晶化结束后,急速冷却、洗涤、干燥滤饼,得到晶化产物,ZSM-5分子筛晶体尺寸为40~200nm,原料中Fe、Mn杂质进入分子筛骨架,得到的ZSM-5分子筛产品同时含有微孔和介孔。其XRD物相结果与实施方式一相同。Using iron tailings as raw materials, the SiO2 content is 67%, take 10 g of iron tailings and activate them in a muffle furnace at 500 ° C for 3 hours, immerse the activation product in water for 1 hour, adjust the pH of the filtrate to 9, stand for 12 hours, and dry The powder was obtained as the raw material for ZSM-5 molecular sieve synthesis. 2g of filter residue, 0.2g of sodium aluminate, 2.5g of Na 2 CO 3 ·10H 2 O and 0.2g of TPABr were placed in a mortar and mixed for 5 minutes. Set to crystallize for 72 hours. After the crystallization is completed, the filter cake is rapidly cooled, washed and dried to obtain a crystallization product. The crystal size of ZSM-5 molecular sieve is 40-200 nm. Pores and Mesopores. The XRD results are the same as those of the first embodiment.

实施例3:Example 3:

以铁尾矿为原料,SiO2含量为67%,取10g铁尾矿在马弗炉中500℃活化3小时,活化产物水浸1小时,调节滤液pH为9,静置12小时,烘干得到粉末作为ZSM-5分子筛合成原料。将2g滤渣、0.2g铝酸钠、2.5g Na2CO3·10H2O以及实施方式一所得ZSM-5分子筛0.2g放置在研钵中研磨混合5分钟,将混合物置入密封的不锈钢反应釜中升温到100℃恒温静置晶化72小时。晶化结束后,急速冷却、洗涤、干燥滤饼,得到晶化产物,ZSM-5分子筛晶体尺寸为40~200nm,原料中Fe、Mn杂质进入分子筛骨架,得到的ZSM-5分子筛产品同时含有微孔和介孔。其XRD物相结果与实施方式一相同。Using iron tailings as raw materials, the SiO2 content is 67%, take 10 g of iron tailings and activate them in a muffle furnace at 500 ° C for 3 hours, immerse the activation product in water for 1 hour, adjust the pH of the filtrate to 9, stand for 12 hours, and dry The powder was obtained as the raw material for ZSM-5 molecular sieve synthesis. 2g of filter residue, 0.2g of sodium aluminate, 2.5g of Na 2 CO 3 ·10H 2 O and 0.2 g of ZSM-5 molecular sieve obtained in Embodiment 1 were placed in a mortar for grinding and mixing for 5 minutes, and the mixture was placed in a sealed stainless steel reactor. The temperature was raised to 100°C in a constant temperature and allowed to stand for 72 hours for crystallization. After the crystallization is completed, the filter cake is rapidly cooled, washed and dried to obtain a crystallization product. The crystal size of ZSM-5 molecular sieve is 40-200 nm. Pores and Mesopores. The XRD results are the same as those of the first embodiment.

实施例4:Example 4:

以金尾矿为原料,SiO2含量为71%,取10g铁尾矿在马弗炉中500℃活化3小时,活化产物水浸1小时,调节滤液pH为9,静置12小时,烘干得到粉末作为ZSM-5分子筛合成原料。将3g滤渣、0.2g铝酸钠、3g Na2CO3·10H2O以及0.2g TPABr放置在研钵中研磨混合5分钟,将混合物置入密封的不锈钢反应釜中升温到100℃恒温静置晶化72小时。晶化结束后,急速冷却、洗涤、干燥滤饼,得到晶化产物,ZSM-5分子筛晶体尺寸为40~200nm,原料中Fe、Mn杂质进入分子筛骨架,得到的ZSM-5分子筛产品同时含有微孔和介孔。其XRD物相结果与实施方式一相同。Using gold tailings as raw materials, the SiO2 content is 71%, take 10 g of iron tailings and activate them in a muffle furnace at 500 ° C for 3 hours, immerse the activation product in water for 1 hour, adjust the pH of the filtrate to 9, stand for 12 hours, and dry The powder was obtained as the raw material for ZSM-5 molecular sieve synthesis. 3g of filter residue, 0.2g of sodium aluminate, 3g of Na 2 CO 3 ·10H 2 O and 0.2g of TPABr were placed in a mortar and mixed for 5 minutes. Crystallize for 72 hours. After the crystallization is completed, the filter cake is rapidly cooled, washed and dried to obtain a crystallization product. The crystal size of ZSM-5 molecular sieve is 40-200 nm. Pores and Mesopores. The XRD results are the same as those of the first embodiment.

实施例5:Example 5:

以金尾矿为原料,SiO2含量为71%,取10g铁尾矿在马弗炉中500℃活化3小时,活化产物水浸1小时,调节滤液pH为9,静置12小时,烘干得到粉末作为ZSM-5分子筛合成原料。将3g滤渣、0.2g铝酸钠、3g Na2CO3·10H2O以及实施方式一所得ZSM-5分子筛0.2g放置在研钵中研磨混合5分钟,将混合物置入密封的不锈钢反应釜中升温到100℃恒温静置晶化72小时。晶化结束后,急速冷却、洗涤、干燥滤饼,得到晶化产物,ZSM-5分子筛晶体尺寸为40~200nm,原料中Fe、Mn杂质进入分子筛骨架,得到的ZSM-5分子筛产品同时含有微孔和介孔。其XRD物相结果与实施方式一相同。Using gold tailings as raw materials, the SiO2 content is 71%, take 10 g of iron tailings and activate them in a muffle furnace at 500 ° C for 3 hours, immerse the activation product in water for 1 hour, adjust the pH of the filtrate to 9, stand for 12 hours, and dry The powder was obtained as the raw material for ZSM-5 molecular sieve synthesis. 3g of filter residue, 0.2g of sodium aluminate, 3g of Na 2 CO 3 ·10H 2 O and 0.2g of ZSM-5 molecular sieve obtained in Embodiment 1 were placed in a mortar for grinding and mixing for 5 minutes, and the mixture was placed in a sealed stainless steel reactor. The temperature was raised to 100°C and the temperature was kept for crystallization for 72 hours. After the crystallization is completed, the filter cake is rapidly cooled, washed and dried to obtain a crystallization product. The crystal size of ZSM-5 molecular sieve is 40-200 nm. Pores and Mesopores. The XRD results are the same as those of the first embodiment.

Claims (5)

1. A method for preparing a ZSM-5 molecular sieve by using solid wastes specifically comprises the following steps:
step 1: mixing a silicon source, sodium carbonate decahydrate, an aluminum source substance and a template agent according to a certain proportion by taking solid waste as the silicon source, and mixing and grinding for 1-10 minutes; wherein the solid waste is rice hull ash, iron tailings or gold tailings; wherein the silicon source, the sodium carbonate decahydrate, the aluminum source and the template agent are in the following proportion: n (TPABr)/n (SiO)2)=0.1~2.0;n(Na2CO3∙10H2O)/n(SiO2)=0.1~10;n(SiO2)/n(Al2O3)=20~+∞;
Step 2: and (3) placing the mixture obtained in the step (1) into a stainless steel reaction kettle, heating to 100-200 ℃, crystallizing for 3-96 hours, and after the crystallization is finished, rapidly cooling, washing and drying a filter cake to obtain the ZSM-5 molecular sieve containing the hierarchical pore structure.
2. The method of claim 1, wherein when iron tailings and gold tailings are used as the silicon source, the iron tailings and the gold tailings are activated.
3. The method according to claim 2, wherein the activation treatment process is: activating gold tailings and iron tailings by adopting an alkali sintering mode, wherein n (NaOH)/n (SiO)2) 1-4, the activation treatment temperature is 200-1000 ℃, and the activation treatment time is 1-10 hours; and mixing and stirring the activated alkali sintering product with water for 50-70 minutes, separating the product into a water-soluble substance and a water-insoluble solid, directly adjusting the pH =9 of the solution without solid-liquid separation, standing for 6-24 hours, and drying at the constant temperature of 80 ℃ to obtain solid powder.
4. The process according to claim 2, wherein the iron or gold tailings have a composition: the iron tailings or the gold tailings mainly contain quartz, albite, potash feldspar, anorthite, magnetite, pyrite, cordierite, talc and illite.
5. The method according to claim 2, characterized in that the iron tailings and the gold tailings are not subjected to acid leaching purification treatment before activation, so that acid-containing waste liquid is avoided.
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